CN112029043B - Photosensitive elastic resin, preparation method thereof and application thereof in photocuring 3D printing technology - Google Patents
Photosensitive elastic resin, preparation method thereof and application thereof in photocuring 3D printing technology Download PDFInfo
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- CN112029043B CN112029043B CN202010785658.3A CN202010785658A CN112029043B CN 112029043 B CN112029043 B CN 112029043B CN 202010785658 A CN202010785658 A CN 202010785658A CN 112029043 B CN112029043 B CN 112029043B
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- 239000011347 resin Substances 0.000 title claims abstract description 67
- 229920005989 resin Polymers 0.000 title claims abstract description 67
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 22
- 238000010146 3D printing Methods 0.000 title claims abstract description 14
- 238000005516 engineering process Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 21
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 31
- 238000011069 regeneration method Methods 0.000 claims abstract description 27
- 230000008929 regeneration Effects 0.000 claims abstract description 25
- 239000007790 solid phase Substances 0.000 claims abstract description 25
- 239000003085 diluting agent Substances 0.000 claims abstract description 9
- 238000007731 hot pressing Methods 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 58
- 229920000728 polyester Polymers 0.000 claims description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 21
- 125000001931 aliphatic group Chemical group 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 229920000570 polyether Polymers 0.000 claims description 21
- 229920002635 polyurethane Polymers 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 11
- 229920001971 elastomer Polymers 0.000 claims description 8
- -1 mercapto phenylboronic acid ester Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- ZXUMDXRBCNYUAY-UHFFFAOYSA-N phenyl(sulfanyloxy)borinic acid Chemical compound SOB(O)C1=CC=CC=C1 ZXUMDXRBCNYUAY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 20
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 244000028419 Styrax benzoin Species 0.000 description 10
- 235000000126 Styrax benzoin Nutrition 0.000 description 10
- 235000008411 Sumatra benzointree Nutrition 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 229960002130 benzoin Drugs 0.000 description 10
- 235000019382 gum benzoic Nutrition 0.000 description 10
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 9
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 9
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 8
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 7
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 7
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 5
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000005251 gamma ray Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- AUVSUPMVIZXUOG-UHFFFAOYSA-N (4-sulfanylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(S)C=C1 AUVSUPMVIZXUOG-UHFFFAOYSA-N 0.000 description 1
- KYNFOMQIXZUKRK-UHFFFAOYSA-N 2,2'-dithiodiethanol Chemical compound OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 description 1
- WNGBEGNWOVUHCN-UHFFFAOYSA-N 2-(2-hydroxyethyldiselanyl)ethanol Chemical compound OCC[Se][Se]CCO WNGBEGNWOVUHCN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 1
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
Abstract
The invention discloses a photosensitive elastic resin, a preparation method thereof and application thereof in a photocuring 3D printing technology, wherein the photosensitive elastic resin is prepared from urethane acrylate, a reactive diluent, a photosensitive functional monomer and a photoinitiator in a certain proportion, the photosensitive functional monomer simultaneously contains a photosensitive group capable of undergoing a photocuring reaction and a dynamic bond with dynamic reversible characteristics, the photosensitive group can participate in the photocuring reaction to form a three-dimensional cross-linking structure, and the dynamic bond endows the cured polyurethane elastomer with solid-phase regeneration performance, so that the polyurethane elastomer can be recycled under certain hot-pressing conditions, and the solid-phase regenerated polyurethane elastomer still has good mechanical properties and high regeneration efficiency.
Description
Technical Field
The invention relates to the technical field of functional polymer materials, in particular to photosensitive elastic resin, a preparation method thereof and application thereof in a photocuring 3D printing technology.
Background
The photocuring technology is a green curing and forming method, and has the advantages of high curing speed, energy conservation, environmental protection and the like. 3D printing is a rapid prototyping technology, and based on a digital model file, materials are molded in a shape designed by a model in a layer-by-layer printing mode to be piled and molded, so that a structure which cannot be realized by a common prototyping technology can be printed. In recent years, photocuring 3D printing combining photocuring technology and 3D printing technology has become a research hotspot, and has a good development prospect due to the combination of the advantages of photocuring and 3D printing.
After the photosensitive resin is subjected to photocuring 3D printing and forming, three-dimensional covalent crosslinking is formed, so that excellent stability is given to the device, but the recovery and regeneration of the photosensitive resin are very difficult, and serious resource waste and environmental pollution are caused. For example, chinese patent CN109232825A provides a 3D printing elastomer photosensitive resin, which is prepared from a polyurethane matrix resin, an active diluent, a functional monomer, a photoinitiator, and the like in a certain ratio, and an elastomer device with a certain mechanical strength can be prepared by 3D printing and photocuring, but the printed and molded device is difficult to dissolve and refractory due to a three-dimensional covalent cross-linking network formed by photocuring cross-linking, so that waste is difficult to recycle.
Disclosure of Invention
The invention aims to solve the technical problems of difficult dissolution and infusibility and difficult recovery and regeneration of the existing photocuring 3D printing elastomer, and provides a photosensitive elastic resin.
Another object of the present invention is to provide a method for preparing a photosensitive elastic resin.
It is still another object of the present invention to provide a use of the photosensitive elastic resin.
It is another object of the present invention to provide a solid-phase-recyclable polyurethane elastomer.
Another object of the present invention is to provide a solid-phase regeneration method of a polyurethane elastomer which can be solid-phase regenerated.
The above purpose of the invention is realized by the following technical scheme:
a photosensitive elastic resin comprises the following components in parts by mass:
40-80 parts of urethane acrylate;
10-40 parts of a reactive diluent;
10-30 parts of photosensitive functional monomer;
0.5-5 parts of a photoinitiator;
the photosensitive functional monomer simultaneously contains a photosensitive group capable of undergoing a photocuring reaction and a dynamic bond with dynamic reversible characteristics.
According to the invention, dynamic bonds with dynamic reversible characteristics are introduced into photosensitive elastic resin, and can be recombined under certain conditions after the dynamic bonds are broken, namely certain reversibility is achieved, so that after the polyurethane elastomer is prepared from the photosensitive elastic resin, due to the fact that the polyurethane elastomer contains the dynamic bonds in a cross-linked network structure, the reversibility of the dynamic bonds is utilized, the solidified polyurethane elastomer can be endowed with solid phase regeneration performance, namely after the polyurethane elastomer is crushed, a large number of dynamic bonds are formed on powder particle interfaces, and under certain hot mold pressing conditions, the dynamic bonds among the particle interfaces are recombined to form new covalent bonds, so that the particle interfaces are connected together, solid phase regeneration of the polyurethane elastomer is realized, and the solid phase regenerated polyurethane elastomer still has good mechanical properties and high regeneration efficiency.
Preferably, the composition is prepared from the following components in parts by mass:
45-60 parts of polyurethane acrylate;
15-30 parts of reactive diluent;
15-25 parts of photosensitive functional monomer;
1-3 parts of a photoinitiator.
Preferably, the photosensitive group capable of undergoing photocuring reaction is an acrylate group and/or a thiol group, and the dynamic bond is one or more of a disulfide bond, a diselenide bond, an acylhydrazone bond, an imine bond, an oxime urethane bond or a borate ester bond.
Preferably, the photosensitive functional monomer is one or more of acrylate containing a disulfide bond, acrylate containing a diselenide bond, acrylate containing an acylhydrazone bond, acrylate containing an imine bond, acrylate containing an oxime urethane bond, and mercapto phenylboronate.
More preferably, the photosensitive functional monomer is one or more of acrylate containing diselenide bonds, acrylate containing oxime urethane bonds and mercapto phenylboronate.
Preferably, the polyurethane acrylate is one or more of polyether aliphatic polyurethane acrylate, polyether aromatic polyurethane acrylate, polyester aliphatic polyurethane acrylate and polyester aromatic polyurethane acrylate.
Preferably, the reactive diluent is one or more of ethoxylated pentaerythritol tetraacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, isobornyl acrylate, hydroxyethyl methacrylate and isooctyl acrylate.
Preferably, the photoinitiator is one or more of benzoin dimethyl ether, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl phenyl ketone and 2-phenyl benzyl-2-dimethyl amine-1- (4-morpholine benzyl phenyl) butanone.
The invention protects the preparation method of the photosensitive elastic resin, which comprises the following steps:
under dark and dark conditions, uniformly mixing the urethane acrylate, the reactive diluent, the photosensitive functional monomer and the photoinitiator to obtain the photosensitive elastic resin.
The invention also protects the application of the photosensitive elastic resin in the photocuring 3D printing technology.
The invention also protects the polyurethane elastomer capable of being regenerated in a solid phase, which is prepared from the photosensitive elastic resin.
The invention also provides a solid-phase regeneration method of the polyurethane elastomer capable of solid-phase regeneration, which comprises the following steps:
and crushing the polyurethane elastomer after photocuring into rubber powder, and carrying out hot pressing for 0.5-1 h at the pressure of 5-10 MPa and the temperature of 30-80 ℃ to obtain the polyurethane elastomer after solid phase regeneration.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a photosensitive elastic resin, which is prepared from polyurethane acrylate, a reactive diluent, a photosensitive functional monomer and a photoinitiator in a certain ratio, wherein a polyurethane elastomer is prepared after photocuring, and a dynamic bond with dynamic reversible characteristics is introduced into a system to endow the cured polyurethane elastomer with solid-phase regeneration performance, so that the solid-phase regeneration of the polyurethane elastomer can be realized under a certain hot-pressing condition, and the solid-phase regenerated polyurethane elastomer still has good mechanical properties and high regeneration efficiency.
Drawings
FIG. 1 is a synthetic route of acrylate monomer having acylhydrazone bond.
FIG. 2 is a synthetic route for an imine bond-containing acrylate monomer.
FIG. 3 is a synthetic route of an acrylate monomer containing an oxime urethane bond.
FIG. 4 shows a synthetic route of acrylate monomers containing borate ester bonds.
FIG. 5 is a synthetic route for disulfide bond-containing acrylate monomers.
FIG. 6 is a synthetic route for acrylate monomers containing diselenide linkages.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents used in the examples of the present invention are those conventionally purchased, unless otherwise specified.
Example 1
A photosensitive elastic resin comprises the following components in parts by mass:
60 parts of polyether aliphatic urethane acrylate, 10 parts of ethoxylated pentaerythritol tetraacrylate, 12 parts of 1, 6-hexanediol diacrylate, 15 parts of acrylate containing an acylhydrazone bond and 3 parts of benzoin dimethyl ether.
The preparation method of the photosensitive elastic resin comprises the following steps:
weighing 50 parts of p-hydroxybenzaldehyde in a four-neck flask, adding 150mL of dried tetrahydrofuran for dissolving, adding 0.22 part of dibutyltin dilaurate, heating to 65 ℃ under the protection of nitrogen, slowly dropwise adding 57.78 parts of isocyanate ethyl acrylate, continuing to react for 4 hours after dropwise adding, obtaining an intermediate product I after the reaction is finished, respectively weighing 20 parts of malonyl hydrazine and 79.7 parts of the intermediate product I in the four-neck flask, adding 300mL of ethanol for dissolving, then adding 9.97 parts of anhydrous sodium sulfate, stirring and reacting for 5 hours at 55 ℃, obtaining acrylate containing acylhydrazone bonds after the reaction is finished (the synthetic route is shown in FIG. 1), wherein the yield is 84%; adding polyether type aliphatic urethane acrylate, ethoxylated pentaerythritol tetraacrylate, 1, 6-hexanediol diacrylate, a photosensitive functional monomer containing an acylhydrazone bond and benzoin dimethyl ether into a three-neck flask, and stirring at a high speed for 0.5h to obtain the photosensitive elastic resin.
Example 2
A photosensitive elastic resin comprises the following components in parts by mass:
40 parts of polyester aliphatic urethane acrylate, 14 parts of trimethylolpropane triacrylate, 25 parts of tripropylene glycol diacrylate, 20 parts of acrylate containing acylhydrazone bonds and 1 part of 2,4, 6-trimethylbenzoyldiphenylphosphine oxide.
The preparation method of the photosensitive elastic resin comprises the following steps:
polyester type aliphatic urethane acrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, acrylate containing acylhydrazone bonds and 2,4, 6-trimethylbenzoyldiphenylphosphine oxide were added to a three-necked flask and stirred at high speed for 0.5h to obtain a photosensitive elastic resin.
Example 3
The photosensitive elastic resin is prepared from the following components in parts by mass:
60 parts of polyester type aliphatic urethane acrylate, 10 parts of isobornyl acrylate, 12 parts of trimethylolpropane triacrylate, 15 parts of imine bond-containing acrylate and 3 parts of 1-hydroxycyclohexyl phenyl ketone.
The preparation method of the photosensitive elastic resin comprises the following steps:
respectively weighing 20 parts of acrylamide and 18.87 parts of terephthalaldehyde into a four-neck flask, dissolving the acrylamide and the terephthalaldehyde in 117mL of ethanol, adding 3.89 parts of anhydrous sodium sulfate, stirring and reacting at 70 ℃ for 4 hours to obtain acrylic ester containing imine bonds (the synthetic route of the acrylic ester is shown in figure 2) after the reaction is finished, wherein the yield is 83%; adding polyester type aliphatic urethane acrylate, isobornyl acrylate, trimethylolpropane triacrylate, imine bond-containing acrylate and 1-hydroxycyclohexyl phenyl ketone into a three-neck flask, and stirring at high speed for 0.5h to obtain the photosensitive elastic resin.
Example 4
The photosensitive elastic resin is prepared from the following components in parts by mass:
40 parts of polyether type aromatic urethane acrylate, 19 parts of hydroxyethyl methacrylate, 20 parts of isooctyl acrylate, 20 parts of imine bond-containing acrylate and 1 part of 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone.
The preparation method of the photosensitive elastic resin comprises the following steps:
adding polyether type aromatic urethane acrylate, 19 parts of hydroxyethyl methacrylate, isooctyl acrylate, imine bond-containing acrylate and 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone into a three-neck flask, and stirring at a high speed for 1h to obtain the photosensitive elastic resin.
Example 5
The photosensitive elastic resin is prepared from the following components in parts by mass:
50 parts of polyester type aromatic urethane acrylate, 10 parts of hydroxyethyl methacrylate, 18 parts of 1, 6-hexanediol diacrylate, 20 parts of oxime urethane bond-containing acrylate and 2 parts of benzoin dimethyl ether.
The preparation method of the photosensitive elastic resin comprises the following steps:
20 parts of dimethylglyoxime is weighed into a four-neck flask, 60mL of dried tetrahydrofuran is added for dissolution, 0.15 part of dibutyltin dilaurate is added, and the temperature is raised to 65 ℃ under the protection of nitrogen. Then, 53.44 parts of isocyano ethyl methacrylate is slowly added dropwise, the reaction is continued for 4 hours after the dropwise addition is finished, and the oxime urethane bond-containing acrylate is obtained after the reaction is finished (the synthetic route is shown in figure 3), wherein the yield is 84%; adding polyester type aromatic urethane acrylate, hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate, oxime urethane bond-containing acrylate and benzoin dimethyl ether into a three-neck flask, and stirring at high speed for 1h to obtain the photosensitive elastic resin.
Example 6
A photosensitive elastic resin comprises the following components in parts by mass:
25 parts of polyether aliphatic urethane acrylate, 25 parts of polyester aliphatic urethane acrylate, 10 parts of isobornyl acrylate, 13 parts of tripropylene glycol diacrylate, 25 parts of acrylate containing oxime urethane bonds and 2 parts of 2,4, 6-trimethylbenzoyl diphenylphosphine oxide.
The preparation method of the photosensitive elastic resin comprises the following steps:
polyether type aliphatic urethane acrylate, polyester type aliphatic urethane acrylate, isobornyl acrylate, tripropylene glycol diacrylate, oxime urethane bond-containing acrylate and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide are added into a three-neck flask and stirred at a high speed for 1h to obtain the photosensitive elastic resin.
Example 7
The photosensitive elastic resin is prepared from the following components in parts by mass:
30 parts of polyether aromatic urethane acrylate, 30 parts of polyester aromatic urethane acrylate, 15 parts of ethoxylated pentaerythritol tetraacrylate, 7 parts of isooctyl acrylate, 15 parts of acrylate containing borate bond and 3 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone.
The preparation method of the photosensitive elastic resin comprises the following steps:
respectively weighing 25 parts of 4-mercaptophenylboronic acid and 11.54 parts of 1,2,4, 5-benzenetetracarboxylic acid into a four-neck flask, adding 110mL of tetrahydrofuran for dissolving, then adding 3.65 parts of anhydrous sodium sulfate, stirring and reacting at 65 ℃ for 6 hours to obtain acrylate containing a boronic acid ester bond (the synthetic route of the acrylate is shown in figure 4) after the reaction is finished, wherein the yield is 84%; adding polyether type aromatic urethane acrylate, polyester type aromatic urethane propylene, ethoxylated pentaerythritol tetraacrylate, isooctyl acrylate, acrylate containing a borate bond and 2-hydroxy-2-methyl-1-phenyl-1-acetone into a three-neck flask, and stirring at a high speed for 1h to obtain the photosensitive elastic resin.
Example 8
A photosensitive elastic resin comprises the following components in parts by mass:
20 parts of polyether aliphatic urethane acrylate, 20 parts of polyester aromatic urethane acrylate, 14 parts of 1, 6-hexanediol diacrylate, 25 parts of tripropylene glycol diacrylate, 20 parts of photosensitive functional monomer prepared from acrylate containing a borate bond and 1 part of benzoin dimethyl ether.
The preparation method of the photosensitive elastic resin comprises the following steps:
polyether aliphatic urethane acrylate, polyester aromatic urethane acrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate and borate ester bond-containing acrylate are added into a three-neck flask to prepare a photosensitive functional monomer, benzoin dimethyl ether and stirred at a high speed for 1h to obtain the photosensitive elastic resin.
Example 9
A photosensitive elastic resin comprises the following components in parts by mass:
20 parts of polyether type aliphatic urethane acrylate, 30 parts of polyester type aromatic urethane acrylate, 15 parts of tripropylene glycol diacrylate, 7 parts of isobornyl acrylate, 20 parts of disulfide bond-containing acrylate and 2 parts of 2-phenylbenzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone.
The preparation method of the photosensitive elastic resin comprises the following steps:
20 parts of bis (2-hydroxyethyl) disulfide are weighed into a four-necked flask, dissolved by adding 60mL of dried tetrahydrofuran, and 0.12 part of dibutyltin dilaurate is added and the temperature is raised to 65 ℃ under nitrogen protection. Then slowly dripping 40.23 parts of isocyano ethyl methacrylate, continuing the reaction for 4 hours after the dripping is finished, and obtaining the acrylic ester containing the disulfide bond (the synthetic route of the acrylic ester is shown in figure 5) after the reaction is finished, wherein the yield is 87%; adding polyether type aliphatic urethane acrylate, polyester type aromatic urethane acrylate, tripropylene glycol diacrylate, isobornyl acrylate, disulfide bond-containing acrylate and 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone into a three-neck flask, and stirring at a high speed for 1h to obtain the photosensitive elastic resin.
Example 10
A photosensitive elastic resin comprises the following components in parts by mass:
20 parts of polyether type aromatic urethane acrylate, 30 parts of polyester type aromatic urethane acrylate, 15 parts of trimethylolpropane triacrylate, 15 parts of isobornyl acrylate, 25 parts of a photosensitive functional monomer containing a disulfide bond and 2 parts of benzoin dimethyl ether.
The preparation method of the photosensitive elastic resin comprises the following steps:
adding polyether type aromatic urethane acrylate, polyester type aromatic urethane acrylate, trimethylolpropane triacrylate, isobornyl acrylate, disulfide bond-containing acrylate and benzoin dimethyl ether into a three-neck flask, and stirring at high speed for 1h to obtain the photosensitive elastic resin.
Example 11
The photosensitive elastic resin is prepared from the following components in parts by mass:
60 parts of polyester type aromatic urethane acrylic acid, 15 parts of trimethylolpropane triacrylate, 10 parts of 1, 6-hexanediol diacrylate, 20 parts of acrylate containing diselenide bonds and 3 parts of 1-hydroxycyclohexyl phenyl ketone.
The preparation method of the photosensitive elastic resin comprises the following steps:
20 parts of bis (2-hydroxyethyl) diselenide are weighed into a four-neck flask, 60mL of dried tetrahydrofuran is added for dissolution, 0.09 part of dibutyltin dilaurate is added, and the temperature is raised to 65 ℃ under the protection of nitrogen. Then slowly dripping 25.02 parts of isocyanoethyl methacrylate, continuing to react for 4 hours after dripping is finished, and obtaining a photosensitive functional monomer containing a diselenide bond (the synthetic route of the photosensitive functional monomer is shown in figure 6) after the reaction is finished, wherein the yield is 86%; adding polyester type aromatic polyurethane acrylic acid, trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, acrylate containing diselenide bond and 1-hydroxycyclohexyl phenyl ketone into a three-neck flask, and stirring at high speed for 1h to obtain the photosensitive elastic resin.
Example 12
The photosensitive elastic resin is prepared from the following components in parts by mass:
60 parts of polyether type aliphatic urethane acrylate, 15 parts of ethoxylated pentaerythritol tetraacrylate, 10 parts of 1, 6-hydroxyethyl methacrylate, 25 parts of acrylate containing diselenide bond and 3 parts of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide.
The preparation method of the photosensitive elastic resin comprises the following steps:
polyether type aliphatic polyurethane acrylate, ethoxylated pentaerythritol tetraacrylate, 1, 6-hydroxyethyl methacrylate, acrylate containing diselenide bonds and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide are added into a three-neck flask and stirred at a high speed for 1h to obtain the photosensitive elastic resin.
Comparative example 1
The photosensitive elastic resin of the present comparative example was prepared from the following components in parts by mass: 60 parts of polyether type aliphatic urethane acrylate, 17 parts of ethoxylated pentaerythritol tetraacrylate, 20 parts of 1, 6-hexanediol diacrylate, 3 parts of benzoin dimethylether and 20 parts of 1, 6-hexanediol diacrylate (acrylate monomer without dynamic bonds). The comparative example was prepared in the same manner as in example 1.
Comparative example 2
The components of the photosensitive elastic resin of this comparative example, the amounts thereof and the preparation method thereof were the same as in example 1, except that the photosensitive functional monomer having an acylhydrazone bond was replaced with 8 parts.
Comparative example 3
The components of the photosensitive elastic resin of this comparative example, the amounts thereof used, and the preparation method were the same as in example 1, except that the photosensitive functional monomer having an acylhydrazone bond was replaced with 35 parts.
Performance testing
1. Test method
(1) The preparation method of the solid-phase renewable polyurethane elastomer comprises the following steps: and pouring the prepared photosensitive elastic resin into a photocuring 3D printer (Formlabs Form 3) for printing, and setting the layer thickness to be 50 mu m to obtain the polyurethane elastomer capable of being solid-phase regenerated.
(2) The preparation method of the polyurethane elastomer regenerated sheet comprises the following steps: and (2) crushing the polyurethane elastomer capable of being solid-phase regenerated prepared in the step (1) into rubber powder, and carrying out hot pressing for 1h at the pressure of 8MPa and the temperature of 60 ℃ to prepare a polyurethane elastomer regenerated sheet.
(3) And cutting the regenerated polyurethane elastomer sheet into a standard dumbbell-shaped sample strip, and performing tensile test at a tensile rate of 50mm/min by using a universal testing machine to obtain the tensile strength and the elongation at break of the sample strip.
Regeneration efficiency (gamma) of tensile strength σ ): is the tensile strength (sigma) of the sample after solid phase regeneration Recycled ) Tensile Strength (σ) of the sample before solid phase regeneration Virgin ) The ratio of the components is as follows: gamma ray σ ＝σ Recycled /σ Virgin 。
Regeneration efficiency of elongation at break (gamma) ε ): elongation at break (. Epsilon.) of the sample after solid phase regeneration Recycled ) Elongation at break (. Epsilon.) of the sample before solid phase regeneration Virgin ) The ratio of the components is as follows: gamma ray ε ＝ε Recycled /ε Virgin And repeating the above operations for the second circulation solid phase regeneration.
2. Test results
Table 1 regeneration efficiency of materials provided in examples and comparative examples
As can be seen from the results in table 1, the solid-phase-regenerated polyurethane elastomers provided in examples 1 to 12 of the present invention have excellent regeneration efficiency of tensile strength and elongation at break, and can still maintain good mechanical properties after being regenerated for 2 cycles, and compared with the photocurable 3D-printed polyurethane elastomer provided in comparative example 1, the regeneration efficiency of comparative example 1 is significantly improved, and the comparative example 1 is replaced by an acrylate monomer without dynamic bonds, so the regeneration efficiency is very low, and the mechanical properties of the regenerated elastomer are poor; comparative example 2 the regeneration efficiency is reduced due to the reduced proportion of the photosensitive functional monomer; comparative example 3 increases the amount of the photosensitive functional monomer, but the crosslinking density decreases after curing and molding due to the bifunctional photosensitive functional monomer, and the mechanical properties of the elastomer also decrease.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (7)
1. The photosensitive elastic resin is characterized by comprising the following components in parts by mass:
45 to 60 parts of polyurethane acrylate;
15-30 parts of an active diluent;
15 to 25 parts of photosensitive functional monomer;
1 to 3 parts of photoinitiator;
the photosensitive functional monomer is one or more of acrylate containing a disulfide bond, acrylate containing a diselenide bond, acrylate containing an acylhydrazone bond, acrylate containing an imine bond, acrylate containing an oxime urethane bond and mercapto phenylboronic acid ester.
2. The photosensitive elastic resin according to claim 1, wherein the photosensitive functional monomer is one or more of acrylate containing diselenide bond, acrylate containing oxime urethane bond, and mercapto phenylboronate.
3. The photosensitive elastic resin according to claim 1, wherein the urethane acrylate is one or more of polyether aliphatic urethane acrylate, polyether aromatic urethane acrylate, polyester aliphatic urethane acrylate and polyester aromatic urethane acrylate.
4. The method for preparing the photosensitive elastic resin according to any one of claims 1 to 3, comprising the steps of:
under dark and dark conditions, uniformly mixing the urethane acrylate, the reactive diluent, the photosensitive functional monomer and the photoinitiator to obtain the photosensitive elastic resin.
5. Use of the photosensitive elastic resin according to any one of claims 1 to 3 in a photocuring 3D printing technology.
6. A solid-phase-recyclable polyurethane elastomer produced from the photosensitive elastic resin according to any one of claims 1 to 3.
7. The solid-phase recycling method of a solid-phase recyclable polyurethane elastomer according to claim 6, comprising the steps of:
and crushing the polyurethane elastomer after photocuring into rubber powder, and hot-pressing for 0.5 to 1h at the pressure of 5 to 10MPa and the temperature of 30 to 80 ℃ to obtain the polyurethane elastomer after solid phase regeneration.
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| CN114149543A (en) * | 2021-12-16 | 2022-03-08 | 江苏富琪森新材料有限公司 | Self-repairing acrylate material and preparation method thereof |
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